X-Ray Diffraction and Crystal Structure

X-Ray Diffraction and Crystal Structure (XRD)

X-ray diffraction (XRD) is one of the most important non-destructive tools to
analyse all kinds of matter - ranging from fluids, to powders and crystals. From
research to production and engineering, XRD is an indispensible method for
structural materials characterization and quality control which makes use of the
Debye-Scherrer method. This technique uses X-ray (or neutron) diffraction on
powder or microcrystalline samples, where ideally every possible crystalline
orientation is represented equally. The resulting orientational averaging causes
the three dimensional reciprocal space that is studied in single crystal diffraction
to be projected onto a single dimension. One describes the three dimensional
space with reciprocal axes x*,y* and z* or alternatively in spherical coordinates q,
*, *. The Debye-Scherrer method averages over * and * and only q remains as
an important measurable quantity. To eliminate effects of texturing and to achieve
true randomness one rotates the sample orientation. In the socalled diffractogram
the diffracted intensity is shown as function either of the scattering angle 2 or as
a function of the scattering vector q which makes it independent of the used X-ray
wavelength. The diffractogram is like a unique fingerprint of materials.
This method gives laboratories the ability to quickly analyze unknown materials
and characterize them in such fields as metallurgy, mineralogy, forensic science,
archeology and the biological and pharmazeutical sciences. Identification is
performed by comparison of the diffractogram to known standards or to
international databases.

Detector

HV

Water Pump and Supply

Data
Output

X-Ray Source
Sample
Electronic Circuit Panel
HV Power Supply

Angle Control

Computer

Utility

Binary ASCII
Conversion

Measurement
Server

Control

Rigaku

Right
Measurement

Wavelength
Table

Display

Rigaku Control
Panel

Miniflex II
Right System

Manual
Measurement

Standard
Measurement

Peak Search

Standard Data
Processing

Integral
Intensity
Multi Record

Application Data
Processing

Present
Position

X-Ray Diffraction (XRD) and Crystal Structure : Required Knowledge

Braggs relation for X-ray scattering

Principles of a Bragg spectrometer

Max von Laue and Bragg method

X-ray tube and X-ray production

Debye-Scherrer technique

X-ray optics, slits, Soller slits,

X-ray reflexion

Crystal lattice and reciprocal space

Lattice parameters

Wavelength discrimination

Identification of compounds

X-ray detectors

Powder Diffraction File (PDF)

Sample preparation

Cambridge

Compare with Neutron Diffraction

Application of the XRD method to

Structural

Database

(CSD)
Electron density determination

different other fields

X-Ray Diffraction and Crystal Structure : Tasks and Goals

Set-up

Measure energy

Produce

Determine

Set-up

Compare energy

Determine

WARNINGS

Determine

Be careful.

Determine energy

Shut down

Determine the

Never touch

Remove source after measurement

The RIGAKU MINIFLEX II

X-ray diffractometer

Vitamins are another group of materials commonly tested with XRD. The wrong
polymorph of a vitamin is usually inert and provides no benefit to the consumer. For
example, the B vitamin pantothenic acid has two polymorphs, one of which is inert. The
data in Figure 2 is from a B-complex vitamin supplement. Using XRD it is possible to
identify each component, and whether the correct polymorph is present to ensure proper
potency.

Measured XRD pattern of a B-complex vitamin supplement

Simulated XRD patterns of cocaine-maltose mixtures

Simulated diffraction patterns of cocaine and maltose are displayed along with the peak
positions of the International Centre for Diffraction Data (ICDD) standard. Two mixtures, 50%
cocaine / 50% maltose and 10% cocaine / 90% maltose, show the qualitative differences in
the XRD pattern as the components are varied. Qualitative identification is based on the
presence of the unique diffraction lines for each substance, the "X-ray fingerprint." In
addition, a quantitative determination can be made for each component by measuring its
peak intensity and comparing it to the intensities measured from one or more samples of
known concentration.

General XRD phase/

composition identification
analysis
General X-ray diffraction
phase/composition identification will distinguish the
major, minor, and trace
compounds present in a
sample. The data usually
includes mineral (common)
name of the substance,
chemical formula, crystalline system, and reference
pattern number from the
ICDD International database. A summary table of
analysis results and diffraction plot with reference
pattern markers for visual
comparison is shown below.

Minor phases

Minor phases

Trace phases

Anhydrite,
CaSO4 - orthorhombic
ICDD # 72-0916

Calcite,
syn CaCO3 - rhombohedral
ICDD # 05-0586

Portlandite,
syn, Ca(OH)2 - hexagonal
ICDD # 44-1181

Gypsum,
syn CaSO4.2H2O - monoclinic
ICDD # 33-031

Brucite,
Mg(OH)2 - hexagonal
ICDD # 74-2220

Quartz,
SiO2 - hexagonal
ICDD # 64-0312